JP6936406B1 - Improved material surface modification - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved surface modification of a material. In one aspect, the present disclosure provides a method of surface modification of a material, wherein (1) the oxidation level of the surface of the material is measured by X-ray photoelectron spectroscopy (XPS). The steps of oxidizing the material so that it falls within a specific numerical range, and (2) A. Steps of grafting the oxidized material and / or B. It comprises the step of treating the oxidized material with a hydrophilic polymer. In one aspect, the present disclosure provides a method of producing a fibrous composite in which a fibrous material is contained within a second material, the method: (1) oxidizing at least one of the fibrous material and the second material. A step of processing, (2) a step of interfacially adhering or adhering the fiber material and the second material after the step of oxidation treatment, and (3) a step of melting the second material to obtain a fiber composite material. include. [Selection diagram] None

Description

The present disclosure relates to surface modification of improved materials. In particular, the present disclosure describes methods of surface modification of materials and materials with improved adhesion between materials, as well as methods of interfacially adhering or adhering to produce adhesive or composite materials and surface modifications so produced. Provided are quality materials, adhesive materials and composite materials. In particular, the present disclosure provides a strong fiber composite material.

In various products such as automobile parts, aircraft parts, medical instruments, and electronic devices, adhesive materials or composite materials formed by integrating different materials are used (International Publication No. 2005/075190, etc.). The strength of the adhesive or composite may be inadequate, especially at the interface between different materials, which may limit the use of the adhesive or composite. Therefore, it is desired to improve the bond strength between different materials.

International Publication No. 2005/075190

The inventor has found suitable surface modification conditions for the material. The inventor has also found a method for tightly bonding different materials. In addition, the inventor has produced unprecedented high-strength adhesives and composites. Based on such findings, the present disclosure describes a method of surface-modifying a material, a material having improved interfacial adhesion between the materials, and a method of producing an adhesive material or a composite material by interfacial adhesion or adhesion, and a method thereof. Provided are surface modification materials, adhesive materials and composite materials prepared as described above.

Accordingly, the present disclosure provides:
(Item 1)
A method of surface modification of a material
(1) A step of oxidizing the material and
(2) A step of surface-coating the oxidized material and
A method comprising the above, wherein the oxidation treatment comprises.
(I) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is only about 1 to 20% of that before the oxidation treatment. Implemented to increase or
(Ii) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is about 5 to 15%. Will be done
(Iii) When measured by X-ray photoelectron spectroscopy (XPS), the O / C atomic number ratio within a depth of 10 nm on the surface of the material is about 0.03 to 0.2. The method to be characterized.
(Item 2)
When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is higher than that before the oxidation treatment. The method of item 1, wherein the method is carried out so as to increase by about 1.5 to 15%.
(Item 3)
When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is higher than that before the oxidation treatment. The method of item 11, wherein the method is carried out so as to increase by about 2-10%.
(Item 4)
When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is about 5 to 15. The method according to item 1, which is carried out so as to be%.
(Item 5)
When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), the O / C atomic number ratio within a depth of 10 nm on the surface of the material is about 0.03 to 0.2. The method according to item 1, which is carried out in 1.
(Item 6)
A step of surface-modifying the material by the method according to any one of items 1 to 5.
A method for producing an adhesive material, which comprises a step of interfacially adhering or adhering the material and a second material.
(Item 7)
The method according to item 6, wherein the step of interfacial adhesion or adhesion is carried out under the condition that an adhesive is present between the material and the second material.
(Item 8)
The method according to item 6 or 7, wherein the step of interfacially adhering or adhering the material and the second material is carried out after about 1 hour has elapsed from the step of surface-modifying the material.
(Item 9)
A test piece obtained by bonding the surface-modified material having a width of 10 mm and a thickness of 1 mm to an aluminum plate having a thickness of 0.2 mm so that the bonding area is 10 mm × 10 mm has a speed of 20 mm / min and a support point of 60 mm. When the tensile test is performed at a short distance, items 6 to 8 bring about an improvement in shear strength of 200 N or more as compared with an adhesive material prepared from a material prepared under the same conditions except that the step of oxidation treatment is not performed. The method according to any one of the above.
(Item 10)
A method for producing a fiber composite material in which a fiber material is contained in a second material.
(1) A step of oxidizing at least one of the fiber material and the second material, and
(2) After the step of the oxidation treatment, a step of interfacially adhering or adhering the fiber material and the second material,
(3) A step of melting the second material to obtain the fiber composite material, and
Including methods.
(Item 11)
The method according to item 10, wherein the second material is a resin material.
(Item 12)
When a three-point bending test is performed on a test piece of the fiber composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm at a speed of 2 mm / min and a distance between support points of 40 mm, the oxidation treatment step is not performed. The method according to item 10 or 11, which provides 1.2 times or more bending strength as compared with a fiber composite material produced under the same conditions except for.
(Item 13)
The oxidation treatment
(I) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is only about 1 to 20% of that before the oxidation treatment. Implemented to increase or
(Ii) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is about 5 to 15%. Will be done
(Iii) When measured by X-ray photoelectron spectroscopy (XPS), the O / C atomic number ratio within a depth of 10 nm on the surface of the material is about 0.03 to 0.2. The method according to any one of items 10 to 12, which is characteristic.
(Item 14)
The method according to any one of items 10 to 13, wherein the weight ratio of the fiber material in the fiber composite material is about 30% or less.
(Item 15)
The method according to any one of items 1 to 14, which comprises a step of washing the material to be oxidized before the step of oxidizing the material.
(Item 16)
Any of items 1 to 15, wherein the oxidation treatment step comprises oxidation treatment by a treatment selected from the group consisting of plasma treatment, ozone treatment, ultraviolet irradiation treatment, corona discharge treatment, high pressure discharge treatment and chemical oxidation. The method described in paragraph 1.
(Item 17)
The step of surface coating is to graft (a) a hydrophilic vinyl monomer to the oxidized material.
The method according to any one of items 1 to 16, which comprises (a) grafting a hydrophilic monomer and applying a hydrophilic polymer, or (c) grafting a vinyl ester monomer and subjecting it to hydrolysis. ..
(Item 18)
The method according to any one of items 1 to 17, wherein the weight increase of the oxidized material by the surface coating step is less than about 5%.
(Item 19)
A surface modification material produced by the method according to any one of items 1 to 5.
(Item 20)
An adhesive material or fiber composite material produced by the method according to any one of items 6 to 18.
(Item 21)
The fiber according to item 20, which is not cut at a breaking point when evaluated by a three-point bending test at a speed of 2 mm / min and a distance between support points of 40 mm for a test piece having a length of 80 mm, a width of 10 mm and a thickness of 2 mm. Composite material.
(Item 22)
An adhesive material in which the first material and the second material are in close contact with each other or adhered to each other.
The cut surface of at least one of the first material side half material and the second material side half material obtained by cutting the adhesive material along the interface between the first material and the second material is X. An adhesive material having a (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material as measured by X-ray photoelectron spectroscopy (XPS), which is about 5 to 15%.
(Item 23)
A fiber composite material that is not cut at a breaking point when evaluated by a three-point bending test at a speed of 2 mm / min and a distance between support points of 40 mm for a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm.
(Item 24)
The fiber composite material according to item 20, 21 or 23, wherein the weight ratio of the fiber material in the fiber composite material is about 30% or less.

In the present disclosure, it is intended that the one or more features described above may be provided in combination in addition to the specified combinations. Further embodiments and advantages of the present disclosure will be appreciated by those skilled in the art upon reading and understanding the following detailed description, as appropriate.

The present disclosure provides high-strength adhesive or composite materials. Adhesive or composite materials using materials that normally do not bond with each other may also be provided.

The FTIR-ATR spectrum of polypropylene samples having different oxidation times is shown. The relationship between the absorbance ratio of the FTIR-ATR spectrum of the polypropylene oxide sample and the oxidation treatment time is shown. The FTIR-ATR spectrum of the strongly oxidized superpolymer polyethylene sample is shown. The relationship between the oxidation time of the polypropylene sample and the (A) C1s narrow spectrum and (B) O1s narrow spectrum in the XPS measurement is shown. The relationship between the ratio of the number of O1s / C1s orbitals obtained from the XPS-narrow spectrum of the polypropylene sample and the oxidation treatment time is shown. The relationship between the type of carbon bond and its ratio (%) obtained from the XPS-narrow spectrum of the polypropylene sample and the oxidation treatment time is shown. The relationship between the oxidation treatment time of the polypropylene sample and the abundance ratio (%) of the number of bound COH is shown. The relative ratio between the atmospheric pressure plasma discharge treatment time of the polypropylene cloth and the tensile shear strength of the sample is shown. The relationship between the ozone treatment time of the polypropylene cloth and the relative strength of the tensile shear strength of the treated sample is shown. The relationship between the oxidation treatment time and the tensile shear strength in a sample in which a DHM-treated polypropylene plate and an aluminum plate are bonded is shown. (A) The weight-displacement curve in the three-point bending test for the fiber composite material of polypropylene (PP) fiber / epoxy resin is shown. (B) The weight-displacement curve in the three-point bending test for the fiber composite material of ultra-high molecular weight polyethylene (UHMWPE) fiber / epoxy resin is shown.

Hereinafter, the present disclosure will be described with reference to the best form. Throughout the specification, it should be understood that the singular representation also includes its plural concept, unless otherwise stated. Therefore, it should be understood that singular articles (eg, "a", "an", "the", etc. in English) also include the plural concept unless otherwise noted. It should also be understood that the terms used herein are used in the meaning commonly used in the art unless otherwise noted. Thus, unless otherwise defined, all terminology and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, this specification (including definitions) takes precedence.

The present disclosure will be described below, if necessary, with reference to the accompanying drawings by way of exemplary embodiments. Throughout the specification, it should be understood that the singular representation also includes its plural concept, unless otherwise stated. It should also be understood that the terms used herein are used in the meaning commonly used in the art unless otherwise noted. Thus, unless otherwise defined, all terminology and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, this specification (including definitions) takes precedence.

The definitions and / or basic technical contents of terms particularly used in the present specification will be described below as appropriate.

(Definition, etc.)
As used herein, the term "composite material" refers to a material formed by integrally molding a plurality of different materials (which may be the same material). For example, the composite material may be a molded product in which the materials are interfacially adhered or adhered to each other, or a molded product in which at least a part of the material is melted or melted and the melted or melted portions are mixed and solidified. In particular, a composite material in which one of the materials is a fiber can be referred to as a fiber composite material. Further, in the present specification, the "adhesive material" refers to a composite material produced by adhesion between materials.

In the present specification, "X-ray photoelectron spectroscopy" (which may be abbreviated as XPS) refers to an analysis method utilizing the emission of photoelectrons when the surface of a sample to be measured is irradiated with X-rays, and refers to the surface layer of the sample to be measured. This method is widely used as a method for analyzing parts. According to XPS, qualitative analysis and quantitative analysis can be performed using the X-ray photoelectron spectroscopic spectrum obtained by analysis on the surface of the sample to be measured. Between the depth from the sample surface to the analysis position (hereinafter, also referred to as "detection depth") and the photoelectron extraction angle, the following equation is generally used:
Detection depth ≒ mean free path of electrons x 3 x sin θ
(In the equation, the detection depth is the depth at which 95% of the photoelectrons constituting the X-ray photoelectron spectroscopic spectrum are generated, and θ is the photoelectron extraction angle.)
Can hold. From the above equation, it is understood that the smaller the photoelectron extraction angle is, the shallower the depth from the sample surface can be analyzed, and the larger the photoelectron extraction angle is, the deeper the part can be analyzed. For example, in an analysis performed by XPS at a photoelectron extraction angle of 10 degrees, the analysis position is usually a very surface layer portion having a depth of about several nm from the sample surface. Among the X-ray photoelectron spectroscopy spectra (horizontal axis: bond energy (eV), vertical axis: intensity) obtained by analysis performed by XPS, for example, the C1s spectrum provides information on the energy peak of the 1s orbit of carbon atom C. Includes. The elemental composition of the material within the measurement range can be determined, for example, by wide scan measurement (scan range: 0 to 1000 eV, energy resolution: 1 eV / step, etc.). The ratio of can be calculated. The binding state of a particular element can be analyzed by narrow scan measurements (scan range: 1s spectral range of that element, energy resolution: 0.1 eV, etc.). For example, in the C1s spectrum, the CH and CC peaks are located at about 284.6 eV, the CN peaks are located at about 285.7 eV, and the CO peaks are located at about 286.1 eV. However, the peak of C = O is located at about 288 eV, and the peak of O—C—O is located at about 289 eV. The position of the eV peak for each bond of other carbon or other elements is known or can be readily determined by one of ordinary skill in the art. XPS analysis can be performed, for example, on a surface with an area of ^{0.1 mm 2 of the material.}

As used herein, the term "resin" refers to a polymer of the same polymerizable compound or a polymer of two or more polymerizable compounds having different structures, and refers to a homopolymer and a copolymer. include.

As used herein, the term "about" refers to the value shown plus or minus 10%, unless otherwise defined. As used for ratio, "about" refers to the ratio of plus or minus 10% of the left value (X) of the indicated ratio (denoted as X: Y, etc.). "About", when used for temperature, refers to the indicated temperature plus or minus 5 ° C.

(Preferable embodiment)
In one aspect, the present disclosure provides a method of surface modification of a material, which: (1) measures the oxidation level of the surface of the material (eg, within 10 nm) by X-ray photoelectron spectroscopy (XPS). This includes a step of oxidizing the material and (2) a step of surface-coating the oxidized material so as to have a specific numerical range. In a preferred embodiment, the oxidation treatment step can be carried out to achieve oxidation levels on the surface of the material that are below detectable levels in the infrared absorption spectrum. The present disclosure also provides a method for producing an adhesive material, which comprises a step of interfacially adhering or adhering a surface-modified material to a second material. As used herein, the term "interfacially adhered" means that the materials are directly bonded to each other. As used herein, "adhering" means bonding materials together via an adhesive.

In one aspect, the present disclosure provides a method of producing a fibrous composite in which a fibrous material is contained within a second material, the method: (1) oxidizing at least one of the fibrous material and the second material. A step of processing, (2) a step of interfacially adhering or adhering the fiber material and the second material after the step of oxidation treatment, and (3) a step of melting the second material to obtain a fiber composite material. include. In a preferred embodiment, the second material is a resin material (including rubber).

In one aspect, the present disclosure provides high-strength composites (eg, fiber composites) at levels previously unattainable.

(material)
In the present disclosure, the material to be interfacially adhered or adhered is not particularly limited, and examples thereof include polymer materials, metals, glass, ceramics, silicon, carbon materials, woods, materials of these composite materials, and any materials among these materials. It is intended to be interfacially adhered or adhered.

In one embodiment, the polymer material (eg, resin (including rubber)) consists of (1) an addition polymer: an olefin, a vinyl compound, a vinylidene compound and other compounds having a carbon-carbon double bond. Homopolymer or copolymer of selected monomer, (2) Fluororesin: Polytetrafluoroethylene, Perfluoroalkoxyalkane, Perfluoroethylene-propylene copolymer, Perfluoroethylenepropene copolymer, Ethylene-tetra Fluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethane, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-perfluorodioxol copolymer, polyvinylfluoride, (3) polycondensate: Polyester (including polyethylene terephthalate and aliphatic and total aromatic polyester), polycarbonate, polybenzoate, polyimide, polyamide (including aliphatic polyamide including nylon and aromatic polyamide), (4) Additive condensate: phenol resin , Urea resin, melamine resin, xylene resin, or polymers thereof, (5) polyaddition products: polyurethane, polyurea, etc., or polymers thereof, (6) ring-opening polymers: cyclopropane, ethylene oxide, Homopolymers or copolymers such as propylene oxide, lactone and lactam, (7) cyclized polymer: divinyl compound (for example, 1,4-pentadiene), diyne compound (for example, 1,6-heptadiine) and the like alone. Polymers or copolymers, (8) isomerized polymers: eg alternating copolymers of ethylene and isobutene, (9) electrolytic polymers: homopolymers or copolymers such as pyrrole, aniline, acetylene, (10). ) Silicon resin, silicon resin, (11) aldehyde or ketone polymer, (12) polyether sulfone, (13) natural polymer: cellulose, protein, polysaccharide and the like. Other polymer materials (eg, resins) include polyacetal, polyphenol, polyphenylene ether, polyalkylparaoxybenzoate, polyimide, polybenzimidazole, poly-p-phenylene benzobisthiazole, poly-p-phenylene benzobisoxazole, polybenzothiazole. , Polybenzoxasol, acetate as the fiber, regenerated cellulose fiber (rayon, cupra, polynosic, etc.), vinylon, fiber of a copolymer of vinyl alcohol and vinyl chloride, and the like.

Ethylene, propylene, butene-1, penten-1 as a vinyl compound as a monomer forming a polymer material (for example, a resin (including rubber)), a vinylidene compound, and other compounds having a carbon-carbon double bond. , Hexen-1,4-methyl-pentene-1, octene-1, vinyl chloride, styrene, acrylic acid, methacrylic acid, acrylic acid or ester of methacrylic acid, vinyl acetate, vinyl ethers, vinyl carbazole, acrylonitrile, vinylidene chloride, Examples thereof include vinylidene fluoride, isobutylene, maleic anhydride, pyromellitic anhydride, 1-butenoic acid, ethylene tetrafluoride, ethylene trifluoride, butadiene, isoprene and chloroprene. Examples of specific polymer materials (for example, resins) include polyester, polypropylene, polyethylene, polyolefin, acrylic, polyvinyl acetate, AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer). , Polycarbonate, Polyethylene terephthalate, Polybutylene terephthalate, Polymethylmethacrylate, Polyallyl diglycol carbonate, Polymer containing butadiene, Synthetic rubber, Polyether ether ketone (PEEK), Rayon, Cupra, Polystyrene (PS), Polyphenylene sulfide (PPS), polyaramid, polyimide, polyamide (nylon), polymethylpentene (TPX (registered trademark) of Mitsui Chemicals, Inc.), vinylon, cotton, linen, silk, wool, and the like.

In one embodiment, the polymer material (eg, resin) may be formed from a single polymer or a mixture of multiple polymers. In one embodiment, the polymeric material (eg, resin) may be thermoplastic or thermosetting.

In one embodiment, the material may have shapes such as fibers, woven fabrics, non-woven fabrics, cloths, boards, films, sheets, tubes, rods, hollow containers, boxes, foams, laminates, etc., but is not particularly limited.

In one embodiment, the material (eg, a polymeric material) may contain additives such as antioxidants, stabilizers, nucleating agents, flame retardants, fillers, foaming agents, antistatic agents and the like. ..

(process)
In one embodiment, the surface of the material may be washed to remove impurities prior to the surface modification treatment. In one embodiment, the solubility parameters of the material and about 0.5-10, eg, about 0.5, about 1, about 1.5, about 2, about 3, about 4, about 5, about 6, about 7. , About 8, about 9, about 10, or a solvent or solvent mixture having SP values that differ by a range between any two of these values. For example, polyolefins, silicon resins, fluororesins, polyvinyl chlorides, polyvinylidene chlorides and the like are preferably washed with alcohol or toluene. Acetate, nylon, polyester, polystyrene, acrylic resin, polyvinyl acetate, polycarbonate, polyurethane and the like are preferably washed with alcohol. Cellulose-based materials such as rayon and cupra are preferably washed with detergent and then with alcohol. In one embodiment, the silicone oil is preferably removed as it can inhibit the oxidation of the material surface during the oxidation treatment steps described herein. To remove the silicone oil, for example, a solvent with a solubility parameter = about 7-10 (eg, about 7, about 8, about 9, about 10 or a range between any two of these values), isopropyl. The surface of the material may be cleaned with a cleaning agent such as alcohol or nex silicon off SP (Nippon Paint). In one embodiment, the material is about 0.05 to 1 times the volume of the material, eg, about 0.05, about 0.1, about 0.2, about 0.3, about 0.4, about 0. It can be washed with a cleaning agent in a volume ranging from .5, about 0.7, about 1x or any two of these values. In one embodiment, the material can be washed with detergent 2-5 times. In one embodiment, cleaning can be performed with a combination of solvent and temperature that does not dissolve the surface of the material.

In one embodiment, the surface of the material may be roughened by scratching (rubbing with a file, etc.) before the surface modification treatment, and this treatment increases the area of interfacial adhesion or adhesion. The strength of the composite material formed can be improved. In one embodiment, the material (particularly the polymeric material) may be impregnated prior to the surface modification treatment. The impregnation treatment is a treatment in which a compound (impregnating agent) having an affinity for the material is brought into contact with the material at a temperature equal to or lower than the softening point of the material, and the impregnating agent is introduced into the surface of the material. It is preferable that the material is not substantially deformed by the impregnation treatment. The impregnant can soak into the amorphous region of the material and create gaps inside the material. The impregnation treatment can facilitate the steps of oxidation treatment, grafting, etc. in the surface modification treatment. Any compound that has an affinity for the material can be used as the impregnating agent. In one embodiment, the impregnating agent is a solvent or solvent mixture having an SP value that differs by about 0.5, about 1, about 2, about 3, about 4 or about 5 from the solubility parameter (SP value) of the material. could be. Even a solvent that dissolves a material at room temperature can be used as an impregnating agent if used at a low temperature and / or for a short time. The impregnating agent can be selected according to the type of material. For example, for the polypropylene material, a mixture of toluene, xylene, decalin, tetraline, cyclohexane, dichloroethane (1 volume) and ethanol (4 volumes) can be used as the impregnating agent. , A mixture of toluene, xylene, α-chloronaphthalene, 1 volume of dichlorobenzene and 1 volume of methanol can be used as an impregnating agent in the polyethylene material, and a mixture of 1 volume of toluene and 10 volumes of methanol is impregnated in the polystyrene material. It can be used as an agent, and a mixture of 1 volume of phenol and 10 volumes of hexane can be used as an impregnating agent for the polyethylene terephthalate material.

In one embodiment, the surface modification of the present disclosure comprises the step of oxidizing the surface of the material. In one embodiment, the oxidation treatment of a material, when measured by XPS, has a surface depth of 10 nm or less (bonds between major elements and oxygen (eg, CO bonds, Si—O bonds, etc.)). )) / (All same elements (eg, carbon, silicon) bonds)% is increased by about 1-20%, about 1.5-15%, or about 2-10% from before the oxidation treatment. obtain. In one embodiment, the oxidation treatment of a material, when measured by XPS, is within a depth of 10 nm on the surface of the material (bonds between major elements and oxygen (eg, CO bonds, Si—O bonds, etc.). )) / (All same elements (eg, carbon, silicon) bonds)% can be such that it is about 3-25%, about 4-20% or about 5-15%.

In one embodiment, in the oxidation treatment of the material, when measured by XPS, the ratio of oxygen atoms in all atoms excluding hydrogen having a depth of 10 nm or less on the surface of the material is about 1 to 20% of that before the oxidation treatment. , Can be implemented to increase by about 1.5-15% or about 2-10%. In one embodiment, in the oxidation treatment of a material, when measured by XPS, the ratio of oxygen atoms to all atoms excluding hydrogen having a depth of 10 nm or less on the surface of the material is about 3 to 25%, about 4 to 4. It can be carried out to be 20% or about 5-15%.

In one embodiment, the oxidation treatment of the material is such that (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the block-shaped polypropylene material material is oxidized when measured by XPS. It can be carried out under conditions that increase by about 1-20%, about 1.5-15%, or about 2-10% from the previous. In one embodiment, the oxidation treatment of the material has a (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the block-shaped polypropylene material as measured by XPS, which is about 3. It can be carried out under conditions such as ~ 25%, about 4-20% or about 5-15%.

In one embodiment, in the oxidation treatment of the material, when measured by XPS, the ratio of oxygen atoms in all atoms excluding hydrogen within a depth of 10 nm on the surface of the block-shaped polypropylene material is higher than that before the oxidation treatment. It can be carried out under conditions that increase by about 1-20%, about 1.5-15% or about 2-10%. In one embodiment, in the oxidation treatment of the material, the ratio of oxygen atoms in all atoms excluding hydrogen within a depth of 10 nm on the surface of the block-shaped polypropylene material is about 3 to 25 when measured by XPS. It can be carried out under conditions such as%, about 4-20% or about 5-15%.

In one embodiment, in the oxidation treatment of the material, the oxygen atom / carbon atom ratio within a depth of 10 nm on the surface of the block-shaped polypropylene material material is about 1 to 20% as compared with that before the oxidation treatment when measured by XPS. , Can be carried out under conditions such as an increase of about 1.5-15% or about 2-10%. In one embodiment, the oxidation treatment of the material has an oxygen atom / carbon atom ratio of about 3 to 25% and about 4 to 4 to a depth of 10 nm or less on the surface of the block-shaped polypropylene material when measured by XPS. It can be carried out under conditions such as 20% or about 5-15%.

The radiation source in the above XPS measurement may be, for example, Cr Kα ray, Al Kα ray, or the like. The angles of incidence in the above XPS measurements can be, for example, about 10 °, about 20 °, about 30 °, about 40 °, about 50 °, about 60 °, about 70 °, about 80 ° or about 90 °. The take-out angles in the above XPS measurements can be, for example, about 10 °, about 20 °, about 30 °, about 40 °, about 50 °, about 60 °, about 70 °, about 80 ° or about 90 °. The number of atoms or the number of bonds in the above XPS measurement can be a value obtained only from the measurement result of 1s. The above XPS measurement can be performed by washing the material after the oxidation treatment.

The degree of oxygen introduction by the oxidation treatment can also be measured by the infrared absorption spectrum. For example, the absorbance of the absorption based on the carbonyl group introduced in the oxidized material and the absorbance of the absorption based on the structure of the unchanged crystal portion. be evaluated by the ratio, for example, when polypropylene materials are introduced ratio of absorbance at absorption of 973 cm ^-1 based on the crystalline portion of methyl groups of the absorbance and unchanged around 1710 cm ^-1 based on the introduced carbonyl groups is oxygen Can be an indicator of. However, the inventors have found that the oxidation treatment to the extent that it can be detected in the infrared absorption spectrum is generally excessive, and rather can reduce the strength of the adhesive material or the composite material, and is measured by X-ray photoelectron spectroscopy (XPS). It has been found that the degree of oxidation treatment is preferable so that the above-mentioned specific numerical range is obtained. Excessive oxidation treatment can result in reduced strength, especially in adhesives or composites using fibrous or film shaped materials. The degree of oxidation treatment can be easily set by those skilled in the art by adjusting the treatment time and the like.

In one embodiment, the method described herein comprises the step of oxidizing the surface of a fibrous material (which may include a film-shaped material as well as a fibrous-shaped material). The fibrous material may be any material and may be, for example, a polymeric material (eg, a resin), a metal, glass, carbon material, or a composite material thereof as described herein. In one embodiment, the material of the fiber material is polyester, polypropylene, polyethylene, nylon, acrylic, polyvinyl acetate, rayon, cupra, vinylon, polystyrene (PS), polyphenylene sulfide (PPS), polyaramid, polyimide or polyamide. could be. In one embodiment, the fibrous material can be a mixed fibrous material in which a plurality of fibrous materials are mixed. In particular, high strength and high dust are produced by producing a fibrous resin composite material using a mixed fiber of a high-strength fiber (carbon fiber, glass fiber, etc.) and a fiber having high toughness (polypoly fiber, etc.). Both sexes can be achieved. In one embodiment, the fibrous material is, but is not limited to, about 10 nm to about 1000 μm, eg, about 10 nm to about 1000 μm, about 100 nm to about 1000 μm, about 1 μm to about 1000 μm, about 10 μm to about 1000 μm, about 100 μm. ~ About 1000 μm, about 10 nm ~ about 100 μm, about 100 nm ~ about 100 μm, about 1 μm ~ about 100 μm, about 10 μm ~ about 100 μm, about 10 nm ~ about 10 μm, about 100 nm ~ about 10 μm, about 1 μm ~ about 10 μm, about 10 nm ~ about It can have a diameter of 1 μm, about 100 nm to about 1 μm or about 10 nm to about 100 nm. The smaller the diameter, the lower the degree of oxidation treatment may be preferable. In one embodiment, the fiber material may be twisted with filaments of fine diameter (eg, about 1 μm to about 100 μm) to form fibers of thicker diameter (eg, about 100 μm to about 1000 μm).

The step of oxidation treatment can be carried out by plasma treatment, ozone treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, chemical oxidation and the like.

Ozone treatment is a treatment that exposes the surface of a material to ozone. The exposure method may be any method such as a method of holding the material in an atmosphere in which ozone is present for a predetermined time, a method of exposing the material in an ozone stream for a predetermined time, and the like. Ozone can be generated by supplying an oxygen-containing gas such as air, oxygen gas, or oxygen-added air to an ozone generator, and the ozone-containing gas is introduced into a container or the like holding a material to generate ozone. Processing can be performed. Conditions such as the ozone concentration in the ozone-containing gas, the exposure time, and the exposure temperature can be determined according to the material so as to obtain the degree of oxidation of the material described in the present specification.

Plasma treatment is a treatment in which a material is placed in a container containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen, air, etc., and exposed to plasma generated by glow discharge. When an inert gas such as argon or neon is present at low pressure, the surface of the material can be attacked by the generated plasma and radicals can be generated on the surface. After that, when exposed to air, the radicals can be combined with oxygen to introduce a carboxylic acid group, a carbonyl group, an amino group, or the like on the surface of the material. Conditions such as the intensity of glow discharge, the time, and the type of gas can be determined according to the material so as to be the degree of oxidation of the material described in the present specification.

The ultraviolet irradiation treatment is a process of irradiating the surface of a material with ultraviolet rays. As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. In one embodiment, the surface of the material may be treated with a UV-absorbing solvent prior to irradiation. Conditions such as the wavelength, intensity, and irradiation time of ultraviolet rays can be determined according to the material so as to be the degree of oxidation of the material described in the present specification. In one embodiment, the wavelength of ultraviolet light can be 360 nm or less.

The high-voltage discharge process is a process in which a high voltage of several hundred thousand volts is applied between a large number of electrodes installed on the inner wall surface of the processing device while moving the material in the tunnel-shaped processing device to discharge the material in the air. .. Conditions such as discharge intensity and time can be determined according to the material so as to be the degree of oxidation of the material described in the present specification.

In the corona discharge process, a high voltage of several thousand volts is applied between a grounded metal roll and a wire-shaped electrode placed at intervals of several mm to generate a corona discharge, and the electrode-roll during this discharge is performed. It is a process of passing the material between them. Conditions such as discharge intensity and time can be determined according to the material so as to be the degree of oxidation of the material described in the present specification.

Chemical oxidation is an oxidation treatment in which a compound having an oxidizing ability (oxidizing agent) is applied to the surface of a material. As the oxidizing agent, those skilled in the art can appropriately select any suitable oxidizing agent in the art.

In one embodiment, the treatment of oxidizing the surface of the material other than the ozone treatment oxidizes the surface by radiating to the material, so that there is a shadowed portion depending on the shape of the material such as a fiber aggregate such as a non-woven fabric. If so, ozone treatment is preferable.

In one embodiment, the surface coating steps include (a) grafting a hydrophilic vinyl monomer to the oxidized material, (b) grafting a hydrophilic monomer and applying a hydrophilic polymer, (c). This includes applying a hydrophilic polymer, (d) applying a hydrophilic polymer and grafting a hydrophilic monomer, or (e) grafting a vinyl ester monomer and subjecting it to hydrolysis. Whether the monomers and polymers are hydrophilic is usually understood by those skilled in the art based on the presence of hydroxyl, carboxyl, phosphate or sulfo groups, or their solubility in water. Specific examples of these monomers and polymers are described elsewhere herein.

In one embodiment, the surface coating step does not substantially increase the weight of the oxidized material. The usual grafting process may also increase the weight of the sample by 10-20%, in which case the graft portion may be detached. On the other hand, the surface coatings of the present disclosure may be preferable because they are less likely to cause such problems. In one embodiment, the surface coating step reduces the weight of the oxidized material to less than about 5%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.2%, or Increase by less than about 0.1%.

In one embodiment, the surface modification of the present disclosure may include the step of grafting a monomer onto the surface of the material. The step of grafting may be carried out after the step of oxidizing the surface or after the step of treating (coating) the material with a polymer. The monomer to be grafted is not limited as long as it can be grafted, but a compound having a carbon-carbon double bond or the like can be used. Examples of the hydrophilic monomer include hydroxyalkyl (meth) acrylates such as (meth) acrylamide, 1-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, and 1-dimethylaminoethyl (meth). ) Acrylate, (alkyl) aminoalkyl (meth) acrylate such as 1-butylaminoethyl (meth) acrylate, alkylene glycol mono (meth) acrylate such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polyethylene Polyalkylene glycol mono (meth) acrylates such as glycol mono (meth) acrylates and polypropylene glycol mono (meth) acrylates, ethylene glycol allyl ethers, ethylene glycol vinyl ethers, (meth) acrylic acids, aminostyrenes, hydroxystyrenes, vinyl acetates, glycidyls. (Meta) acrylate, allyl glycidyl ether, vinyl propionate, N, N-dimethylmethacrylate, N, N-diethylmethacrylate, N- (1-hydroxyethyl) methacrylicamide, N-isopropylmethacrylicamide, methacryloylmorpholine, N -Vinyl-1-pyrrolidone, N-vinyl-3-methyl-1-pyrrolidone, N-vinyl-4-methyl-1-pyrrolidone, N-vinyl-5-methyl-1-pyrrolidone, N-vinyl-6-methyl- 1-Pyrrolidone, N-vinyl-3-ethyl-1-pyrrolidone, N-vinyl-4,5-dimethyl-1-pyrrolidone, N-vinyl-5,5-dimethyl-1-pyrrolidone, N-vinyl-3, 3,5-trimethyl-1-pyrrolidone, N-vinyl-1-piperidone, N-vinyl-3-methyl-1-piperidone, N-vinyl-4-methyl-1-piperidone, N-vinyl-5-methyl- 1-piperidone, N-vinyl-6-methyl-1-piperidone, N-vinyl-6-ethyl-1-piperidone, N-vinyl-3,5-dimethyl-1-piperidone, N-vinyl-4,4- Dimethyl-1-piperidone, N-vinyl-1-caprolactam, N-vinyl-3-methyl-1-caprolactam, N-vinyl-4-methyl-1-caprolactam, N-vinyl-7-methyl-1-caprolactam, N-vinyl-7-ethyl-1-caprolactam, N-vinyl-3,5-dimethyl-1-caprolactam, N-vinyl N-vinyllactam such as -4,6-dimethyl-1-caprolactam, N-vinyl-3,5,7-trimethyl-1-caprolactam, N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl -N-ethylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylphthalimide, N-vinylamide, vinylacetic acid, 1-butenoic acid, 2-butenoic acid , Ethylenesulfonic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylamide, vinylpyridine, vinylpyrrolidone, vinylcarbazole, maleic anhydride, pyromellitic anhydride. Examples of the monomer having lower hydrophilicity include vinyl monomers such as acrylic acid ester, methacrylic acid ester, vinyl acetate ester, and styrene. It can be grafted using one monomer or a mixture of multiple monomers.

Monomer grafting involves (1) addition of a catalyst or initiator (hereinafter collectively referred to as "initiator"), (2) heating in the presence or absence of an initiator, and (3) catalyst or initiator. It can be carried out by irradiation with ultraviolet rays in the presence or absence of. As initiators, peroxides (benzoyl peroxide, t-butylhydroxyperoxide, di-t-butylhydroxyperoxide, etc.), azo compounds (2,2'-azobisisobutyronitrile), dicerium ammonium nitrate (IV) ), Persulfate (potassium persulfate, ammonium persulfate, etc.), oxidation-reduction system initiator (oxidizer: persulfate, hydrogen peroxide, hydroperoxide, etc.), inorganic reducing agent: copper salt, iron salt, sodium hydrogen sulfite , Sodium thiosulfate, etc., or organic reducing agent: combination with alcohol, amine, oxalic acid, etc., or oxidizing agent: hydroperoxide, etc., inorganic reducing agent: copper salt, iron salt, sodium hydrogen sulfite, sodium thiosulfate, etc. Alternatively, an organic reducing agent: dialkyl peroxide, diacyl peroxide, etc. and a reducing agent: a tertiary amine, naphthate, mercaptan, an organic metal compound (triethylaluminum, triethylboron, etc.), etc.), and other known radicals. A polymerization initiator can be mentioned. In the case of ultraviolet irradiation, a photosensitizer such as benzophenone or hydrogen peroxide may be added as a catalyst in addition to the initiator. In one embodiment, a vinyl monomer having an amide group may be used, and the amide group may be transferred to Hoffman by the method described in JP-A-8-109228.

For the grafting of the monomer, a general grafting method can be used. A specific example is shown below. In the case of a water-soluble initiator, dissolve the required amount in water. In the case of a water-insoluble initiator, it is dissolved in an organic solvent (acetone, methanol, etc.) that is mixed with water, such as alcohol or acetone, and then mixed with water so that the initiator does not precipitate. Materials and monomers are added to the initiator solution for grafting. In one embodiment, the inside of the processing vessel is replaced with nitrogen. In one embodiment, it is grafted under heating and / or UV irradiation.

In one embodiment, the surface modification of the present disclosure comprises the step of treating (eg, coating) the surface of the material with a polymer. Examples of polymers used in this step are polyvinyl alcohol, carboxymethyl cellulose, ethylene-vinyl alcohol copolymer, polyhydroxyethyl methacrylate, poly-α-hydroxyvinyl alcohol, polyacrylic acid, poly-α-hydroxyacrylic acid, polyvinyl. Examples thereof include pyrrolidone, polyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.), sulfonates thereof, sodium alginate, starch, silk fibroin, silk sericin, gelatin, various proteins, polysaccharides and the like.

In one embodiment, the step of treating the surface of the material with a polymer can be carried out in the presence of a catalyst or initiator. The catalyst and initiator can be similar to the initiator in monomeric grafting. In one embodiment, this step is performed by adding a solution containing the polymer (eg, an aqueous solution) to the material. For example, the material is placed in a solution containing the polymer and initiator and heated to temperatures such as 10-80 ° C, 60-90 ° C.

In one embodiment, the surface modification of the present disclosure comprises cleaning the excess polymer adhering to the surface. For example, the material treated with the hydrophilic polymer may be boiled and washed with an aqueous solution of sodium fatty acid (concentration 1 to 10% by weight) for 1 to 10 minutes, and then washed well with water. In one embodiment, when the total reflection infrared absorption spectrum of the surface of the material treated with the hydrophilic polymer after cleaning is measured, the infrared absorption spectrum is between the infrared absorption spectrum and the infrared absorption spectrum of the material subjected to the oxidation treatment only. It can be washed to the extent that there is no difference in infrared rays. When treated with a poorly hydrophilic monomer or polymer, such as methyl methacrylate or a polymer thereof, or vinyl acetate or a polymer thereof, wash with chloroform at 40 ° C. for 10 to 60 minutes, and then use chloroform or acetone. Can be washed with methanol. In one embodiment, in the total reflection infrared absorption spectrum measurement, the absorption of the treated material by the carbonyl group in the ^{vicinity of 1710 cm-1} is observed to increase the absorbance by about 0 to 5% as compared with the material obtained by the oxidation treatment alone. Wash to a degree. In one embodiment, the material can be effectively cleaned by heating and then cleaning with an ultrasonic cleaner. In one embodiment, the degree of cleaning and the cleaning agent used can be appropriately set by those skilled in the art using the strength of the adhesive or composite material as an index.

In one embodiment, the surface-modified material according to the methods of the present disclosure can be interfacially adhered or adhered to a second material to form an adhesive material. In one embodiment, the material surface-modified by the methods of the present disclosure may be the same material as the second material or may be a different material. In one embodiment, the second material may be surface modified (eg, surface modified by the methods of the present disclosure). In one embodiment, an adhesive may or may not be used in the step of interfacially adhering or adhering to the second material. As the adhesive, any known adhesive such as starch, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl alcohol, epoxy resin, and polymerizable cyanoacrylate can be used. In one embodiment, the step of interfacially adhering or adhering to the second material is to apply a small amount of a solvent capable of dissolving both the surface-modified material and the second material by the method of the present disclosure to adhere the coated portion. It may be carried out by letting it. Although interfacial adhesion or adhesion to polytetrafluoroethylene or polyimide can be relatively difficult, strong adhesive or composite materials made from these materials can also be achieved according to the methods of the present disclosure. The material surface-modified by the method of the present disclosure does not immediately interfacially adhere or adhere to the second material and takes time (eg, about 30 minutes to about 30, about 30 minutes a day, about 1 hour, about 2 hours, About 5 hours, about 10 hours, about 15 hours, about 20 hours, about 1 day, about 2 days, about 5 days, about 10 days, about 15 days, about 20 days, about 25 days, about 30 days, etc.) Even after a lapse of time, it can be firmly bonded to the second material. Therefore, the material itself whose surface has been modified by the method of the present disclosure is also an object of the present disclosure.

In one embodiment, the present disclosure provides a method of producing a fibrous composite material in which the fibrous material is contained within a second material. In one embodiment, the fibrous material in this method may have the characteristics of the fibrous material in the step of oxidizing the surface of the fibrous material described herein. In one embodiment, the method comprises (1) oxidatively treating at least one of the fibrous material and the second material, and (2) interfacial adhesion between the fibrous material and the second material after the oxidative treatment step. It includes a step of bonding and (3) a step of melting the second material to obtain a fiber composite material. In one embodiment, the second material can be a semi-solid material such as rubber, but melting of the second material in such cases refers to, for example, increasing fluidity by subjecting it to high temperatures. It does not necessarily have to be accompanied by a phase change from solid to liquid. In this embodiment, the second material is typically a thermoplastic, such as polyester, polypropylene, polyethylene, polyolefin, acrylic, polyvinyl acetate, AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile). -Butadiene-styrene copolymer), polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, polyallyl diglycol carbonate, copolymer containing butadiene, synthetic rubber, polyether ether ketone (PEEK), rayon, cupra, It can be a resin such as polystyrene (PS), polyphenylensulfide (PPS), polyaramid, polyimide, polyamide (nylon), polymethylpentene (Mitsui Chemicals' TPX®), vinylon, silicon and the like. In one embodiment, the second material can be a soft material such as rubber. In one embodiment, the second material may have a shape that increases the contact area with the fibrous material such as powder, granules, film, etc. in order to strengthen the bond in step (2). In one embodiment, in step (2), the material may be subjected to pressure (eg, pressing) and / or heating. In one embodiment, both the fibrous material and the second material are oxidized. Melting of the second material can be carried out at any suitable temperature, and in one embodiment it is carried out below the temperature at which the second material is modified or decomposed. In one embodiment, the method comprises (1) oxidizing the fibrous material and (2) mixing the fibrous material with a second material (fluid) before curing after the oxidizing step. (3) Includes a step of subjecting the mixture of step (2) to conditions under which the second material is cured. In this embodiment, the second material is typically a thermosetting resin (eg, an epoxy resin). In this embodiment, the conditions for curing the second material can be appropriately determined by those skilled in the art depending on the second material used.

(Composite material)
In one aspect, the present disclosure provides high strength composites (eg, fiber composites). Since the method of the present disclosure can significantly improve the interfacial adhesion between materials, it is possible to provide a high-strength composite material. In one aspect, the composites of the present disclosure (eg, fiber composites) are at break points (where the load on the instrument is significantly reduced when the load is increased in a bending or tensile test). Alternatively, it can be characterized by not being cut beyond the breaking point. The fibers and the second material can each have the materials, shapes and / or properties described in the method of making the fiber composites described herein. In one embodiment, the weight percentage of the fibrous material in the composites of the present disclosure can be about 40% or less, about 30% or less, about 20% or less, about 10% or less, or about 5% or less. Even when a smaller proportion of the fiber material than the conventional fiber composite material is used, the composite material of the present disclosure can have sufficient strength, which may be preferable in production and may cause a problem. It can also have the advantage that the processing load can be reduced.

In one embodiment, the composites of the present disclosure may have high strength not previously achieved. In one embodiment, the composite material of the present disclosure is a three-point bending test or a three-point bending test at a speed of 2 mm / min and a distance between support points of 40 mm on a test piece of the composite material having a length of 80 mm, a width of 10 mm and a thickness of 2 mm. When a tensile test is performed, the material is not cut at or beyond the fracture point (eg, at a displacement distance or load point increased by 5% or 10% from the fracture point) and the material is at least partially connected. .. In one embodiment, the composite material of the present disclosure is subjected to a three-point bending test at a speed of 2 mm / min and a distance between support points of 40 mm on a test piece of the composite material having a length of 80 mm, a width of 10 mm and a thickness of 2 mm. When this is done, it is about 1.1 times or more, about 1.2 times or more, about 1.5 times or more, about 1.7 times as compared with the composite material prepared under the same conditions except that the step of oxidation treatment is not performed. It has more than double or more than double the bending strength. In one embodiment, the composite material of the present disclosure is subjected to a three-point bending test at a speed of 2 mm / min and a distance between support points of 40 mm on a test piece of the composite material having a length of 80 mm, a width of 10 mm and a thickness of 2 mm. When this is done, the bending strength is improved by about 10 MPa or more, about 20 MPa or more, about 50 MPa or more, about 70 MPa or more, or about 100 MPa or more as compared with the composite material produced under the same conditions except that the step of oxidation treatment is not performed. Bring.

In one embodiment, the composite material of the present disclosure is subjected to a tensile test on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm at a tensile speed of 20 mm / min and a distance between support points of 40 mm. In this case, it is about 1.1 times or more, about 1.2 times or more, about 1.5 times or more, and about 1.7 times as much as the composite material prepared under the same conditions except that the step of oxidation treatment is not performed. It has a tensile shear strength of more than or about twice or more. In one embodiment, the composite material of the present disclosure is subjected to a tensile test on a test piece of the composite material having a length of 80 mm, a width of 10 mm, and a thickness of 2 mm at a tensile speed of 20 mm / min and a distance between support points of 40 mm. In this case, the tensile shear strength is improved by about 50 kgf or more, about 70 kgf or more, about 100 kgf or more, or about 200 kgf or more, as compared with the composite material produced under the same conditions except that the step of oxidation treatment is not performed.

In one embodiment, the composite material of the fibers and the second material of the present disclosure is for a test piece 80 mm long, 10 mm wide, 2 or 3 mm thick, at a speed of 2 mm / min and a distance between support points of 40 mm. When evaluated by a three-point bending test, the strength of the second material alone is about 1.1 times or more, about 1.2 times or more, about 1.5 times or more, about 1.7 times or more, or about 2 times or more. Can have bending strength of. Since the resin composite material of the present disclosure (for example, a fiber-resin composite material) has high interfacial adhesion between the materials, the same or different types of resins are further mixed with the resin portion while maintaining the strength of the composite material. (For example, by mixing the melted resins together). Therefore, the resin composite material of the present disclosure (for example, a fiber-resin composite material) can be used not only as a final product but also as a core material, and can be used for producing various molded products.

In one embodiment, the adhesive material obtained by interfacially adhering or adhering the first material and the second material is a first material obtained by cutting the adhesive material along the interface between the first material and the second material. For the cut surface of at least one of the side half material and the second material side half material, the oxygen atom / carbon atom ratio and / or the oxygen atom / carbon atom ratio within a depth of 10 nm of the material surface as measured by X-ray photoelectron spectroscopy (XPS). (CO bond) / (total carbon bond)% can be such a value achieved on the material surface by the oxidation treatment steps of the present disclosure. In one embodiment, the interface-adhesive or adhered adhesive material of the first and second materials is the first material obtained by cutting the adhesive material along the interface between the first and second materials. Oxygen atoms in all atoms except hydrogen within a depth of 10 nm of the material surface when measured by X-ray photoelectron spectroscopy (XPS) on the cut surface of at least one of the side half material and the second material side half material. The percentage and / or (CO bond) / (total carbon bond)% increase when compared to the region of the central portion of the material is achieved at the material surface by the oxidation treatment steps of the present disclosure. It can be the value of increase when compared to the same untreated material.

(Surface modification material)
In one aspect, the present disclosure provides materials surface-modified by the methods of the present disclosure. In one embodiment, the surface modified material is used as an adhesive material to provide an adhesive material or composite material. The material surface-modified by the method of the present disclosure can provide a high-strength adhesive material or composite material without being molded into the adhesive material or composite material immediately after the surface modification, so that the materials can be interfacially adhered to each other. Surface-modifying materials prior to gluing may also be useful. In one embodiment, the surface modified material can be used for purposes other than providing an adhesive or composite material, for example, the methods of the present disclosure provide surface modification without compromising the strength of the material. Surface-modified materials may be suitable for coatings (eg, coatings with hydrophilic materials) as they may allow for quality. Such coated surface modification materials are also contemplated in the present disclosure.

In one embodiment, the surface-modified material of the present disclosure is a surface-modified material having a width of 10 mm and a thickness of 1 mm, which is bonded to an aluminum plate having a thickness of 0.2 mm so that the bonding area is 10 mm × 10 mm. When a tensile test was performed on the test piece at a speed of 20 mm / min and a distance between support points of 60 mm, it was compared with an adhesive material prepared from a material prepared under the same conditions except that the step of oxidation treatment was not performed. The surface is modified so as to bring about an improvement in shear strength of about 150 N or more, about 200 N or more, about 250 N or more, about 300 N or more, about 350 N or more, about 400 N or more, or about 450 N or more.

(Use)
The adhesive materials, composite materials or surface modified materials of the present disclosure can be used for any purpose, for example, parts of transportation vehicles (automobiles, aircraft, etc.), parts of medical equipment, dental materials, building materials. , Surface coating, laminates, etc. In addition, the adhesive material, composite material or surface-modified material of the present disclosure can be suitably used in any application in which the adhesive material or each material constituting the composite material is used. The methods of the present disclosure also provide adhesives, composites or surface modified materials for these applications.

The present disclosure has been described above with reference to preferred embodiments for ease of understanding. Hereinafter, the present disclosure will be described based on examples, but the above description and the following examples are provided for purposes of illustration only and not for the purpose of limiting the present disclosure. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in the present specification, but is limited only by the claims.

In the following examples, the polymerization inhibitor contained in the monomer reagent was simply adsorbed and removed by passing the monomer reagent through a glass column filled with activated carbon. Basically, grafting was performed in a nitrogen atmosphere.

[Example 1: Evaluation of oxidation by FTIR and XPS measurement]
The oxidized material was evaluated by FTIR measurement and XPS measurement, respectively.

-Oxidation treatment A polypropylene plate (10 mm x 80 mm x 0.5 mm) (AS ONE 61-6034-78) was oxidized by plasma treatment in the atmosphere. The device used an atmospheric pressure plasma device (Kai Semiconductor (Kyoto) desktop direct type TK-50) connected to a sample feeding device manufactured independently, and the output scale was set to 60 V (maximum scale 130).

-Analysis by Fourier transform infrared spectroscope (FTIR) After washing the oxidized sample with a solvent (nax silicon off SP: Nippon Paint) and water and drying it, Fourier transform infrared spectrophotometer IRPrestige-21 (Shimadzu Seisakusho (Kyoto)) ), The measurement was performed by the total reflection method (ATR). The results are shown in FIGS. 1 and 2.

It is said that the FTIR ATR method can measure the bonding state within a depth of about 10 μm from the surface. FIG. 1 shows the spectra of six samples having different oxidation times. Generally, in the case of oxidation of a sample, a carbonyl group is generated, so a change in absorbance near the ^{absorption band of the carbonyl group, 1730 cm -1, is observed.} In FIG. 1, no significant difference in absorbance near ^{1730 cm -1 is observed.}

In order to compare the absorbances relatively, the absorbance ratio "1730 cm ^-1 absorbance / 1440 cm ^-1 absorbance" was obtained using the absorbance of the ^{absorption peak 1440 cm -1} , which is almost unchanged in the strong oxidation process, as the denominator. The relationship with the oxidation time is plotted in FIG. The absorbance ratio is dispersed with respect to the oxidation treatment time, and no correlation is observed. From the comparison with the results of XPS described later, it was judged that the trace amount of oxidation preferable for this surface treatment is difficult to measure with the sensitivity of FTIR-ATR.

It was confirmed by measuring the ultra-high molecular weight polyethylene (UHMWPE) sample that an increase in absorbance of ^{1727 cm -1} was observed by IR measurement when strong oxidation treatment was performed ignoring the destruction of the material. (Fig. 3).

-Analysis by X-ray photoelectron spectroscopy (XPS) The polypropylene sample measured by the ATR method of FTIR was measured by an X-ray photoelectron spectroscopy analyzer (XPS). The results are shown in FIGS. 4, 5, 6 and 7. The XPS measurement was a condition under which the bonding state at a depth of about 10 nm or less from the surface could be measured. The conditions for XPS analysis were as follows.
Equipment: PHI-5000 VersaProbeII (ULVAC-PHI, Inc., Kanagawa), Radioactive source: CrKα ray, AlKα ray, Extraction angle: 90 °.

FIG. 4 shows (A) C1s narrow spectrum and (B) O1s narrow spectrum in XPS measurement of polypropylene samples having different oxidation treatment times. Table 1 shows the relationship between the abundance of C1s (%), the abundance of O1s (%), and the O / C atomic number ratio determined from the spectrum.

Table 2 shows the types of carbon bonds obtained by waveform analysis of the C1s narrow spectrum and their abundance ratios.

Based on these results, the relationship between the O / C atomic number ratio and the oxidation treatment time is shown in FIG. 5 from the results in Table 1, and the relationship between the ratio of each bond and the oxidation treatment time is shown in FIG. 6 from the results in Table 2. rice field. Further, in FIG. 7, (COH bond%) / (total carbon bond%) was enlarged and plotted.

As the oxidation treatment time increases, the number of C—C and C—H bonds decreases, while the O / C atomic number ratio, C—O—H bond, C = O bond, and O = CO It was confirmed that the number of bonds increased in each case. Although the change in oxygen bond with the oxidation treatment time could not be confirmed by the FTIR measurement of FIGS. 1 and 2, it was found that the oxidation state can be confirmed by the XPS measurement. From FIGS. 5, 6 and 7, it can be seen that when the oxidation treatment time is 10 seconds / cm ² or more, the increase in the carbon-oxygen bond amount becomes gradual.

[Example 2: XPS measurement of ozone-oxidized polyphenylene sulfide fiber]
Polyphenylene sulfide (PPS) fibers (torque converter (registered trademark), Toray, Tokyo) were treated with ozone oxidation and XPS measurement was performed. As the X-ray photoelectron spectroscopy analyzer, K-Alpha (radioactive source: AlKα ray, extraction angle: 90 °) manufactured by Thermo Fisher Scientific (USA) was used.

Table 3 shows the results of XPS surface analysis of untreated and ozone-oxidized PPS fibers. It was confirmed that the O / C atomic number ratio of PPS fibers was increased by the ozone oxidation treatment, and that the C—O—H bond and the OC = O bond were increased.

The ozone oxidation treatment in this example was carried out according to the following procedure.
・ Ozone oxidation treatment Put the test piece in a hard glass container (with gas inlet and outlet) with a volume of 2 L, and use an ozone generator (ON-1-2 type manufactured by Nippon Ozone Co., Ltd.) to generate ozone at 2 g / h. Ozone-containing oxygen at a concentration of 40 g / m ³ was blown into the sample at a flow rate of 1000 ml / min for 20 minutes. Next, ozone-free oxygen was blown in for 10 minutes. The ozone concentration was determined by iodine titration.

In the analysis of the oxidation of the polymethylpentene (PMP) resin sheet and the XPS measurement of the treated sample, the oxidation treatment also increases the O / C atomic number ratio, and the C—O—H bond and the OC = O bond. Was confirmed to increase.
-PMP resin sheet: thickness 0.5 mm, TPX (registered trademark) resin (Mitsui Chemicals, Tokyo)

[Example 3: Change in strength of polypropylene cloth due to plasma discharge oxidation]
Next, a polypropylene multifilament cloth (plain weave cloth made of twisted threads of microfilaments having a diameter of 0.25 mm: size width 100 mm, length 200 mm, thickness 0.6 mm, grain size 20 g / m ² ) is subjected to plasma discharge. It was oxidized. Plasma discharge was performed for 15 seconds, 30 seconds, 60 seconds, and 150 seconds, respectively, per 1 cm ^{2 area.} The plasma discharge device was carried out in the same manner as in Example 1. A tensile strength test was performed after the oxidation treatment.

-Tensile strength test tester: A universal tester AUTOGRAPH AGS-H (Shimadzu, Kyoto) was used, the tensile speed was 10 mm / min, and the distance between test piece support points was 600 mm.

The results are shown in FIG. The vertical axis is the relative strength of the material when the untreated material strength is 100%. As the oxidation treatment time increases, the material strength decreases. In this case, since the sample is a fine fiber, the strength may be significantly reduced. It was confirmed that when this fiber cloth having an oxidation time of 10 seconds / cm ² or less was used as a reinforcing material for a composite material, the material strength was increased. Further, if the polypropylene material is in the form of a plate having a thickness of 0.1 mm or more, the decrease in material strength due to oxidation of ^{20 seconds / cm 2 or less is negligible.}

[Example 4: Decrease in material strength due to ozone oxidation]
A polypropylene multifilament cloth (plain weave cloth made of twisted yarns of 0.25 mm diameter microfilaments: size width 100 mm, length 200 mm, thickness 0.6 mm, grain size 20 g / m ² ) was ozonolyzed. Next, the tensile strength was tested

-Ozonolysis treatment The same procedure as in Example 2 was carried out.
-Tensile strength test The same as in Example 3 was performed.

The results are shown in FIG. Similar to the plasma oxidation treatment, the long-term oxidation treatment caused a decrease in tensile strength. Since the time axis of FIG. 9 is in minutes as compared with FIG. 8, the decrease in material strength due to oxidation is milder in the ozone treatment than in the plasma treatment under the conditions of the ozone treatment performed.

[Example 5: DHM treatment and XPS measurement of sample]
The DHM (Durable Hydrophilic Modification) treatment is completed by performing a surface coating step on the oxidized material. For the plasma oxidized sample (irradiation time 5 seconds / cm ² ), XPS measurement was performed on the sample subjected to the surface coating step. The results are shown in Table 4. It was confirmed that the O1s / C1s ratio and the ratio of each functional group containing oxygen increased in each sample as compared with the sample obtained only by plasma treatment.

The oxidation treatment and coating steps in the DHM treatment in this example were carried out according to the following procedure.
-Oxidation treatment By the method of atmospheric pressure plasma treatment of Example 1, a sample oxidized at an irradiation amount of ^{10 seconds / cm 2 was washed with methanol and water.}
-Coating step A reaction solution A of 400 water, 100 methanol, 1 acrylic acid, and 0.1 methyl methacrylate is prepared by volume ratio. The oxidation-treated material is placed in a flat tray, the reaction solution A is added over the treated material to a depth of about 5 mm, and the lid is covered with a hard glass plate having a thickness of 0.5 mm (sealed). No), UV irradiation ^* was performed from a distance of 100 mm for 20 minutes. The material was taken out, washed with methanol, and then the treated material was sufficiently washed with hot water and dried to complete the treatment. The weight increase of the sample after the treatment was 0.1% or less with respect to the weight of the sample before the treatment.
^* Ultraviolet irradiation: A high-pressure mercury lamp (manufactured by Toshiba Lighting & Technology Corporation, trade name H1500L, total length 360 mm, emission length 200 mm, lamp voltage 315 V, lamp power 1500 W) is irradiated to the sample without a filter. To avoid heating, a homemade "cooling fan with slits in the blower" blows strong air between the lamp and the sample.

[Example 6: Adhesive strength test for searching for the optimum oxidation treatment for DHM treatment]
In order to know the "oxidation time of the oxidation step" of the DHM treatment, which is effective for improving the adhesiveness, the tensile shear strength of the sample in which the polypropylene (PP) plate and the aluminum plate, which have been subjected to DHM treatment with different oxidation times, are bonded with an epoxy adhesive, is determined. It was measured.

The PP plate (size 10 mm × 80 mm, thickness 1.0 mm) was DHM-treated by an oxidation treatment and a coating step according to the following procedure.
-Oxidation treatment The same as in Example 1, plasma discharge was performed. The oxidation treatment was 0 to 20 seconds / cm ² .
-Coating step The coating step of Example 5 was performed.

Adhesion and tensile shear strength were measured according to the following procedure.
-Adhesive tensile shear strength test The treated PP plate and aluminum plate (thickness 0.2 mm) were adhered using Bond Quick 5 (Konishi, Osaka), which is an epoxy adhesive, according to the manufacturer's instructions. That is, after mixing approximately equal amounts of liquid A (main agent; epoxy resin) and liquid B (curing agent; polythiol) on an adhesive mixing sheet, the mixture is applied to a polypropylene sample and the adhesive area is 10 mm × 10 mm. It was evenly applied so that an aluminum plate was placed on top of it (the amount of adhesive was about 80 mg). This adhesive sample was sandwiched between plastic plates, a 1 kg weight was placed on the sample, and the sample was left at room temperature for 36 hours. A tensile test was conducted under the following conditions, and the tensile shear strength (N) was measured.
Equipment used: Desktop load tester FTN1-13A (Aiko Engineering Co., Ltd.), Tensile speed: 20 mm / min, PP plate 4 cm-adhesive part 1 cm-aluminum plate 1 cm exists in the space between holders, PP plate And both ends of the aluminum plate were fixed with a holder, and a tensile test was performed.

The results are shown in FIG. In the figure, the boxed area is the area where material fracture was observed during the adhesion test. It can be said that the modified sample having an oxidation treatment of 3-7 seconds / cm ² has the highest adhesive strength because PP material destruction was observed. In the surface-modified sample of the oxidation treatment 3, 4, 6, 7 seconds / cm ² , the material of the PP plate was destroyed by the numerical value of the strength in FIG. On the other hand, in the modified sample having an oxidation treatment of 5 seconds / cm ² , the adhesive portion did not peel off, the PP plate was stretched, and the measurement became impossible at a stress of 425 N. It can be said that the modified sample having an oxidation treatment of 5 seconds / cm ² is the most preferable adhesion because the PP plate is stretched. At an oxidation time of around 3-7 seconds / cm ² of the oxidation treatment, the adhesive strength of the modified sample is low, but the adhesive strength is higher than that of the untreated sample.

From the results of XPS measurement and adhesive strength test of polypropylene, a material with an oxidation level of O / C atom number ratio of about 0.03 to 0.30 and CO bond rate of about 3 to 20% when measured by XPS. Or, when measured by XPS, the ratio of O atoms (the ratio of O atoms to the atoms excluding hydrogen) is increased by about 0.01 to 0.15 or about 1 to 15% as compared with the untreated material. It is considered that a material having an oxidation level showing an increase in the C—O—H bond ratio can be particularly preferably used for improving the adhesiveness of the material. The decrease in the strength of the material is almost 0% in the case of a plate, and is decreased by 2 to 3% in the case of fine fibers. It has been confirmed that the strength of fine fibers increases when modified fibers are used as composite materials. Therefore, it can be said that the decrease in material strength at the same oxidation level does not have to be regarded as a problem. A similar view was confirmed for materials other than polypropylene.

[Example 7: Durability of processing]
It is said that the plasma-treated silicone rubber sheet loses its adhesiveness unless it is bonded immediately after the treatment. Therefore, the plasma-treated silicon rubber sheet and the DHM-treated silicon rubber sheet were left to stand for a predetermined time, and then adhered to an aluminum plate, and the adhesive tensile shear strength thereof was compared. For comparison, an untreated silicone rubber sheet and an aluminum plate were also bonded. The results are shown in Table 5. The plasma-treated silicone rubber sheet loses its adhesiveness unless it is adhered within about 1 hour. In addition, the adhesive strength is considerably smaller than that of the DHM-treated sample.

The oxidation treatment and the DHM treatment in this example were carried out according to the following procedure.
-Oxidation treatment Plasma treatment; using Kasuga Denki Real Plasma APJ-500 (high frequency power supply AGI-B202) in air and under atmospheric pressure, output = 300W, 200V, sample-electrode distance = 10mm, for the sample. The irradiation was 5 seconds / cm ^{2 (irradiation to 1 cm 2 of the} sample area for 1 second). The degree of oxidation was the same as that of the method of Example 6.
-The following coating steps were performed on the material obtained by oxidizing the DHM-treated silicone rubber sheet by the above plasma treatment. The oxidizing material was placed in the reaction solution and heated at 80 ° C. for 10 minutes. Specifically, a reaction solution obtained by adding 10 mg of azobisisobutyronitrile (AIBN) to a solution of water 800, methanol 200, hydroxyethyl methacrylate (HEMA) 1 and methyl methacrylate (MMA) 0.1 in terms of volume ratio. make. It was placed in a reaction solution and heated at 80 ° C. for 10 minutes. The material was taken out from the reaction mixture, washed with methanol, boiled and washed with water, and dried.

(Fiber resin composite material (FRP) using thermosetting resin (epoxy resin) as the base material)
[Example 8: Composite material of polypropylene fiber and epoxy resin]
FRP of untreated or modified polypropylene (PP) fiber / epoxy resin was made. The bending strength of each sample was measured. The results are shown in Table 6. Even if there was a slight decrease in fiber strength due to modification, the material strength of the produced FRP increased.

The materials used in this example were as follows.
-Polypropylene (PP) fiber; polypropylene plain weave cloth, specific gravity = 20 g / m ² , constituent yarn: multifilament (diameter 0.5 mm), monofilament fiber diameter = 30 μm
-Epoxy resin; Main agent: Liquid epoxy resin, Hardener: Diamine-based hardener: GM-6800 (Brennie Giken, Gunma)

The DHM treatment, the FRP production method, and the test method in this example were as follows.
-DHM treatment Similar to the DHM treatment of Example 5, but the oxidation time is 5 seconds / cm ² .
・ FRP manufacturing method of PP fiber / epoxy resin Hand lay-up method: Six PP cloths are laminated in a stainless steel mold (concave mold), and epoxy resin mixed with a curing agent is poured and left for one day. And solidified. The size of the molded portion (concave mold) of the molding die was 80 mm in length and 10 mm in width; manufactured according to JIS standards. The size of the manufactured FRP = 10 mm x 80 mm x 2.6 mm.
-Material tensile shear strength test Measured using a universal testing machine AUTOGRAPH AGS-H (Shimadzu Corporation, Kyoto).
・ Three-point bending strength test of material (JIS-K7171 compliant)
The same tester was used. Bending speed: 5 mm / min, distance between fulcrums: 40 mm.

[Example 9: Composite material of UHMWPE fiber and epoxy resin]
FRPs of untreated or modified ultra high molecular weight polyethylene (UHMWPE) fibers / epoxy resins were made. The bending strength of each sample was measured. The results are shown in Table 7. Similar to the PP fiber / epoxy resin FRP, the fiber strength decreased slightly due to the modification, but the material strength increased when the FRP was used.

The materials used in this example are as follows.
-Ultra high molecular weight polyethylene (UHMWPE) fiber; multifilament yarn (diameter 0.62 mm) made of monofilament (diameter = 30 μm): Provided by Toyobo Co., Ltd., trade name Dyneema.

The oxidation treatment, coating step, and FRP production method in the DHM treatment in this example were as follows. The three-point bending strength test is the same as in Example 8.
-Oxidation treatment The ozone oxidation method of Example 2 was used. The oxidation treatment time was 15 minutes.
-Coating step The same as the coating step of Example 5 was performed.
・ FRP manufacturing method of UHMWPE fiber / epoxy resin Hand lay-up method: 40 threads are put in parallel in a JIS compliant molding mold (concave mold), and 10 g of epoxy resin mixed with a curing agent is poured into 1 It was left for a day to solidify. The size of the molded FRP = 10 mm x 80 mm x 2.6 mm.

FIG. 11 shows the “load-displacement curve” in the three-point bending strength test corresponding to Tables 6 and 7; (A) is PP fiber / epoxy resin and (B) is UHMWPE fiber / epoxy resin. The untreated PP fiber / epoxy resin and untreated UHMWPE fiber / epoxy resin were split in two in the 3-point bending test, but the DHM-treated PP fiber / epoxy resin and DHM-treated UHMWPE fiber / epoxy resin were bent at 3 points. After the strength test, it remained bent in a "dogleg" shape and did not separate into two. It shows that the adhesion between the fiber and the resin interface is high.

(Composite material using thermoplastic resin as the base material)
For various materials surface-modified according to the method of the present disclosure, composite materials with various materials were prepared and material tests were conducted. In a composite material prepared from an untreated or oxidized fiber or film and a base resin, the material was destroyed by pulling out the fiber or film from the resin in a three-point bending strength test. On the other hand, in the composite material made from the DHM-treated fiber or film and various resins, it was observed that the fiber or film did not come off from the resin and the material was cut while maintaining the adhesiveness, resulting in material destruction. ..

[Example 10: Composite material of PET fiber and polypropylene resin]
A fiber composite material was prepared by combining PET fibers (polyethylene terephthalate; plain woven fabric (NBC Meshtec, Tokyo)) and polypropylene (PP) resin. Then, the same 3-point bending test as described above was performed. The results are shown in Table 8.

The oxidation treatment, the DHM treatment, and the method for producing the composite material in this example were as follows. The three-point bending strength test is the same as in Example 8.
-Oxidation treatment Plasma treatment; PET fibers and PP resin were treated in the same manner as in the plasma treatment of Example 6.
-For the DHM-treated oxidized material, the coating step of Example 7 was performed.
-Composite manufacturing method Spray the mold release agent on the mold. Next, polypropylene resin and PET fiber are alternately packed. The die is fixed to the AS ONE small heat press machine HC300-01, and the temperature is set to 240 ° C. every 10 minutes in a no-pressure state, and then a pressure of 2 MPa is applied for 5 minutes. Then, the temperature is returned to room temperature, and the composite material sample is removed from the mold. The mold was designed based on the JIS standard. The sample size was 60 mm in length, 10 mm in width, and about 2 mm in thickness.

[Example 11: Composite material of carbon fiber and polypropylene resin]
A high-strength fiber composite material was prepared from carbon fiber and polypropylene (PP) resin.

Fiber composite materials having different fiber contents were prepared from carbon fiber (CF) and PP film, and a three-point bending test of the fiber composite material was performed. For carbon fiber, we obtained Mitsubishi Chemical products. The results are shown in Table 9.

The oxidation treatment, the DHM treatment, and the method for producing the composite material in this example were as follows. The three-point bending strength test is the same as in Example 8.
-Oxidation treatment Plasma treatment; carbon fibers (with resin) and polypropylene film were subjected to the same plasma oxidation as in Example 1.
-For the DHM-treated oxidized material, the coating step of Example 7 was performed.
-Manufacturing method of composite material 10 PP films with a thickness of 0.3 mm and a bundle of carbon fiber filaments are packed in a mold. The die is fixed to the AS ONE small heat press machine H300-01, and the temperature is set to 240 ° C., every 10 minutes in a no-pressure state, and then a pressure of 2 MPa is applied and the mixture is left for 5 minutes. Then, the temperature is returned to room temperature and the sample is removed from the mold.

Fiber composite materials made from surface-modified fibers and resins exhibited high bending strength. Fiber composites made from surface-modified fibers and resins showed maximum strength at a small fiber content of 20%.

[Example 12: Composite material of carbon fiber and amide resin]
A high-strength fiber composite material was prepared from carbon fiber and amide resin.

A fiber composite material of surface-modified carbon fiber (CF) and polyamide (PA6) resin was prepared, and a three-point bending test of the fiber composite material was performed. The results are shown in Table 10.

The materials used in this example are as follows.
・ Carbon fiber; Mitsubishi Chemical product obtained ・ Polyamide resin; Sigma-Aldrich PA11 = Nylon-11 pellets

The oxidation treatment and DHM treatment in this example were as follows. The three-point bending strength test is the same as in Example 8.
-Oxidation treatment The carbon fiber (with resin) and PA6 were treated in the same manner as in the ozone treatment of Example 2.
-For the DHM-treated oxidized material of CF, the coating step of Example 7 was performed.
-DHM treatment of PA6 The following coating step was performed on the material subjected to the above oxidation treatment. A reaction solution A of water 400, methanol 400, and a hydrophilic monomer (vinylpyrrolidone ^{*) is prepared by volume.} The treatment material is placed in a flat plate type tray, the reaction solution A is added over the treatment material to a depth of about 5 mm, and the treatment material is covered with a hard glass plate having a thickness of 0.5 mm (sealed). No), UV irradiation was performed from a distance of 100 mm for 10 minutes. The material was removed and washed with methanol. Next, the hydrophilic polymer aqueous solution B ^** was applied to the material, dried, and then boiled and washed with water.
^* Vinyl pyrrolidone; 1-vinyl-2-pyrrolidone, Fujifilm Wako Pure Chemical Industries, Ltd .: Product code 228-01285
^** Hydrophilic polymer aqueous solution B; 1 wt% aqueous solution of a mixture of ^{polyvinylpyrrolidone (PVP) ***} and carboxymethyl cellulose (CMC) ^{*** (mixed weight ratio 10: 1).
***} PVP; Average molecular weight 40,000; K30 Fujifilm Wako Pure Chemical Industries, Ltd .: Product code 161-03105
^*** CMC; Sodium Carboxymethyl Cellulose (Fuji Film Wako Pure Chemical Industries, Ltd. Product Code 4987481229082)

[Example 13: Composite material of polyimide film and polyester resin]
A composite material was similarly prepared from a polyimide (PI) film and a polyester resin, and a three-point bending test of the composite material was performed. The results are shown in Table 11.

The materials used in this example are as follows.
Polyimide (PI) film; AS ONE, Polyimide film Kapton (R), model number 3-1966-07. Thickness 0.25 mm
-Polyester resin: PROST Co., Ltd., unsaturated polyester resin for FRP repair, low shrinkage type, with curing agent, for general lamination (non-paraffin)

The oxidation treatment and DHM treatment in this example were as follows. The three-point bending strength test is the same as in Example 8.
-Oxidation-treated PI film was polished 5 times only one way with water-resistant abrasive paper (particle size 600, water-resistant paper; Belle Starr Abrasive Material Industry STARCKE (Germany)). Next, the ozone treatment of Example 2 was performed.
-DHM treatment For the material subjected to the above oxidation treatment, the coating step was performed as follows. Polymerization after electron beam irradiation was performed as follows. ^{The polished ozone-treated material is irradiated with an electron beam (EB) for 5 seconds / cm 2} (per sample area) under the conditions of an acceleration voltage of 80 kV and an irradiation dose of 250 kGy using an electron beam irradiation device (EC90 manufactured by Iwasaki Electric Co., Ltd.). bottom. The material was taken out, coated with a monomer solution (mixed solution of HEMA10, MMA1, water 10, and methanol 4) by volume, and heated at 60 ° C. for 1 minute. The treatment material was taken out, washed with water and dried.

[Example 14: Composite material of high-strength fiber cloth and vulcanized black rubber]
An untreated or treated high-strength aramid fiber cloth was sandwiched between vulcanized black rubber before curing, and then a cured fiber-rubber composite material was prepared and a T-type peeling test was performed. The results are shown in Table 12.

The materials used in this example are as follows.
-Aramid fiber cloth; Esco Co., Ltd. Size 1.0x1.0m: Kevlar fiber 100 cloth EA911AV-1, thickness 0.5 mm.
・ Vulcanized black rubber; provided by Sulfur Co., Ltd.

The oxidation treatment, the DHM treatment, and the method for producing the composite material in this example were as follows.
-Oxidation treatment Chemical reaction treatment; Take a volume of 10 ml of a sodium hypochlorite solution (Fuji Film Wako Pure Chemical Industries, Ltd. product code 197-02206, effective chlorine: 5.0 +%) and use it as an aqueous solution with 100 ml of water. Put in a glass container and put the material to be processed. After gradual heating, 0.2 ml of acetic acid was added, boiling was carried out for 3 minutes, and the mixture was allowed to cool to room temperature, and then the material was taken out. The material was washed with water and air-dried. It was confirmed by XPS measurement that the material was oxidized.
-DHM treatment The following coating step was performed on the material subjected to the above oxidation treatment. The monomer solution was prepared as a mixed solution of acrylic acid (AA) 10, methacrylic acid (MA) 1, water 10, and methanol 4 by the method of Example 7.
-Production method of composite material A vulcanizing agent was added, an aramid fiber sample was sandwiched between still soft black rubber, a silicone rubber plate was placed on it, and the mixture was pressurized with a weight of 1 kilogram and left for 24 hours. The fiber content was 20%.

The T-type peeling test was performed as follows.
1) Fiber cloth sample size Width 10 mm, length 100 mm
2) Put a cloth between two pieces of black rubber, pull out about 10 mm from the end of the cloth, and heat-mold. The adhesive area between the cloth and rubber is 10 mm x 90 mm.
3) Peel off one end of the black rubber (the side where the cloth is sticking out) by about 10 mm by hand.
4) The peeled rubber end and the protruding part of the cloth were fixed to a jig for a tensile test, and the rubber was pulled at a pulling speed of 10 mm / min.

By the surface modification of the present disclosure, a high-strength composite material having an unprecedented fiber-resin interface can be obtained.

The present disclosure provides benefits in a variety of industries such as automobiles, aircraft, medical appliances, electronic devices, etc., as it provides superior strength surface modification materials and high strength composite materials.

Claims (14)

A method of surface modification of a material
(1) A step of oxidizing the material and
(2) A step of surface-coating the oxidized material and
A method comprising the above, wherein the oxidation treatment comprises.
(I) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is only about 1 to 20% of that before the oxidation treatment. Implemented to increase or
(Ii) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is about 5 to 15%. Will be done
(Iii) When measured by X-ray photoelectron spectroscopy (XPS), the O / C atomic number ratio within a depth of 10 nm on the surface of the material is about 0.03 to 0.2. As a feature ,
The surface coating step is applied to the oxidized material.
(A) Grafting a hydrophilic vinyl monomer,
(B) Graft a hydrophilic monomer and apply a hydrophilic polymer, or
(C) A method comprising grafting a vinyl ester monomer and subjecting it to hydrolysis. A method of surface modification of a material
(1) A step of oxidizing the material and
(2) A step of surface-coating the oxidized material and
A method comprising the above, wherein the oxidation treatment comprises.
(I) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is only about 1 to 20% of that before the oxidation treatment. Implemented to increase or
(Ii) When measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is about 5 to 15%. Will be done
(Iii) When measured by X-ray photoelectron spectroscopy (XPS), the O / C atomic number ratio within a depth of 10 nm on the surface of the material is about 0.03 to 0.2. As a feature,
A method in which the weight increase of the oxidized material by the surface coating step is less than about 5%. When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is higher than that before the oxidation treatment. The method according to claim 1 or 2 , wherein the method is carried out so as to increase by about 1.5 to 15%. When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is higher than that before the oxidation treatment. The method of claim 1 or 2 , wherein the method is carried out so as to increase by about 2-10%. When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), the (CO bond) / (total carbon bond)% within a depth of 10 nm on the surface of the material is about 5 to 15. The method according to claim 1 or 2 , which is carried out so as to be%. When the step of oxidizing the material is measured by X-ray photoelectron spectroscopy (XPS), the O / C atomic number ratio within a depth of 10 nm on the surface of the material is about 0.03 to 0.2. The method according to claim 1 or 2 , which is carried out in 1. A step of surface-modifying the material by the method according to any one of claims 1 to 6.
A method for producing an adhesive material, which comprises a step of interfacially adhering or adhering the material and a second material. The method according to claim 7 , wherein the step of interfacial adhesion or adhesion is carried out under the condition that an adhesive is present between the material and the second material. Approximately one hour after the step of surface modifying the material, a step of interfacially adhering or adhering the material to the second material is performed , where "about" is the indicated value plus or minus 10%. the pointing method of claim 7 or 8. A test piece obtained by bonding the surface-modified material having a width of 10 mm and a thickness of 1 mm to an aluminum plate having a thickness of 0.2 mm so that the bonding area is 10 mm × 10 mm has a speed of 20 mm / min and a support point of 60 mm. If a tensile test was carried out between the distance, the but for the step of oxidizing process in comparison with the adhesive material made from material prepared in the same conditions, results in improved shear strength of at least 200 N, claim 7 The method according to any one of 9. The method according to any one of claims 1 to 10 , further comprising a step of washing the material to be oxidized before the step of oxidizing the material. Any of claims 1 to 11 , wherein the oxidation treatment step includes oxidation treatment by a treatment selected from the group consisting of plasma treatment, ozone treatment, ultraviolet irradiation treatment, corona discharge treatment, high-pressure discharge treatment, and chemical oxidation. The method described in item 1. A surface modification material produced by the method according to any one of claims 1 to 6. Adhesive materials manufactured by the method according to any one of claims 7-12.

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